CN116875882A - 一种690MPa级抗H2S应力腐蚀油套管用卷板及其制造方法 - Google Patents
一种690MPa级抗H2S应力腐蚀油套管用卷板及其制造方法 Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B15/00—Arrangements for performing additional metal-working operations specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B3/02—Rolling special iron alloys, e.g. stainless steel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
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- C21—METALLURGY OF IRON
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- C21D11/00—Process control or regulation for heat treatments
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
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Abstract
本发明涉及油套管生产技术领域,尤其涉及一种690MPa级抗H2S应力腐蚀油套管用卷板及其制造方法。其化学成分按重量百分比为:C:0.13%~0.17%,Si:0.15%~0.30%,Mn:1.40%~1.70%,P:≤0.013%,S:≤0.004%,Ti:0.01%~0.03%,Nb:0.06%~0.10%,V:0.04%~0.08%,Mg:0.005%~0.007%,Zr:0.001%~0.004%,稀土元素:0.001%~0.003%,Al:0.02%~0.06%,N:≤0.008%,其余为Fe和不可避免元素。材料的强度高,低温韧性更好,抗SSC性能优异,可防止油井管的脆断,具有更高的安全性。卷板的最终组织为针状铁素体;Pcm低于0.25%,A/B/C/D类夹杂物级别1.0级以下,各类和值级别1.5级以下,带状组织0.5级以下,‑10℃冲击功大于180J。
Description
技术领域
本发明涉及油套管生产技术领域,尤其涉及一种690MPa级抗H2S应力腐蚀油套管用卷板及其制造方法。
背景技术
油套管是油田最常用的石油专用管材之一,用量大,花费高,是油气田钻采作业中必不可少的施工材料。HFW(高频焊接)套管与无缝管相比,具有壁厚均匀、尺寸精度高、射孔性能好、抗挤毁能力强、成本低等显著优势,正在逐渐替代传统的无缝钢管。
随着人口数量的不断增加,世界能源需求的增长也日益显著,天然气产量一直保持高速增长态势,油套管腐蚀与防护问题逐渐成为人们普遍关注的重点。油套管的H2S腐蚀已成为油气田面临的主要腐蚀类型,已给油田造成了巨大的经济损失,如停工停产、增加维修费用,而且所造成的后果严重,如污染环境,甚至危机生命。开发出具有良好耐腐蚀性的油套管具有重大社会和经济意义。
抗拉强度为690MPa级别的卷板,属于API Spec 5CT规定的N80钢级。API Spec 5CT规定:N80级别屈服强度在552-758MPa之间,抗拉强度≥689MPa,伸长率≥19%;0℃时横向夏比冲击功≥60J。抗H2S应力腐蚀性能SSC按照NACE TM0177规定采用A法A溶液加载72%名义屈服强度载荷下试样经过720小时不开裂。由于N80直缝焊油套管要求进行电阻焊,所以要求良好的焊接性能,冷裂纹敏感系数Pcm尽可能低;为了保证抗冲击和挤压,需要具有一定的冲击韧性;为了保证抗HIC性能,需要控制夹杂物和组织细小、均匀性程度;为保证强度,需要添加一定合金细化晶粒和提供淬透性。
综上所述,既要保证抗拉强度为690MPa级别的卷板强度高,具有良好的焊接性能,抗SSC性能优异;同时保证钢管低温韧性更好,成为丞待解决的技术问题。
发明内容
为了克服现有技术的不足,本发明提供一种690MPa级抗H2S应力腐蚀油套管用卷板及其制造方法。材料的强度高,低温韧性更好,抗SSC性能优异,可防止油井管的脆断,具有更高的安全性。
为了达到上述目的,本发明采用以下技术方案实现:
一种690MPa级抗H2S应力腐蚀油套管用卷板,其化学成分按重量百分比为:
C:0.13%~0.17%,Si:0.15%~0.30%,Mn:1.40%~1.70%,P:≤0.013%,S:≤0.004%,Ti:0.01%~0.03%,Nb:0.06%~0.10%,V:0.04%~0.08%,Mg:0.005%~0.007%,Zr:0.001%~0.004%,稀土元素:0.001%~0.003%,Al:0.02%~0.06%,N:≤0.008%,其余为Fe和不可避免元素。
卷板的最终组织为针状铁素体;Pcm低于0.25%,A/B/C/D类夹杂物级别1.0级以下,各类和值级别1.5级以下,带状组织0.5级以下,-10℃冲击功大于180J。
一种690MPa级抗H2S应力腐蚀油套管用卷板的制造方法,具体包括如下步骤:
1)冶炼连铸:
铁水预处理。
转炉冶炼经顶吹或顶底复合吹炼。
炉外精炼、LF炉轻脱硫处理及进行钙处理,
板坯连铸制成连铸坯,连铸采用电磁搅拌或动态轻压下;
2)轧制:
连铸板坯经加热炉加热至1210~1280℃,随后采用热机械轧制,
粗轧终轧温度1020~1060℃,精轧开轧温度960~990℃,终轧温度830~880℃;
3)冷却:
轧后采用层流冷却,冷却速度为26~30℃/s;
4)卷取:
冷却后进行卷取,卷取温度400~450℃。
与现有技术相比,本发明至少具有如下技术效果或优点:
1、本发明C:0.13%~0.17%,既保证材料的硬度,又保证其焊接性、塑性和冲击韧性;Mg:0.005%~0.007%,有效保证钢的强度和抗HIC、SSC性能;Nb:0.06%~0.10%,保证冲击韧性;Ti:0.01%~0.03%,保证整管热处理后的强度满足N80高强度性能要求,且合金成本低;V:0.04%~0.08%,提高钢的淬透性。具有固溶强化作用,有效提高强度。具有细化晶粒作用,所以对低温冲击韧性有利。与碳形成碳化物,在高温高压下可提高抗氢腐蚀能力。
本发明采用低碳含镁的Nb-V-Ti复合设计,材料的强度高,低温韧性更好,抗SSC性能优异;
2、本发明加入Mg细化夹杂物,可有效改变夹杂物形态和大小,含镁氧化物,该结构细小弥散分布在钢中,形成符合夹杂物,显著提高抗腐蚀性,提升SSC性能和抗冲击性。
3、本发明同时Nb、V、Ti联合作用,可有效控制Pcm在0.25%以下,同时有效提高强度和韧性,且提高抗SSC性能。
4、本发明Pcm低于0.25%,焊接性良好。现有的N80普遍采用C含量0.20%以上,Mn含量1.4%以上,Pcm超过0.25%。Pcm值大于0.25时,冷裂倾向明显增大,可焊性降低。Pcm越低焊接性越好,本发明低于0.25%,焊接性优良。
5、本发明控制粗轧终轧温度1020-1060℃,精轧开轧温度960-990℃,终轧温度830-880℃,该温度范围有利于Nb、V、Ti不同阶段各自析出,细化晶粒尺寸,提高强度和韧性。
6、本发明轧后钢带以26-30℃/s的速度进行冷却,该冷却速度下,获得完全的针状铁素体,该组织明显提高强度和韧性,还可以提高抗HIC性能良。对细化最终组织有利,减少制管时包申格效应造成的屈服强度下降,还可以减轻带状组织到0.5级以下,明显提高强度,同时提高韧性和耐腐蚀性能。
7、本发明冷却后进行卷取,卷取温度400-450℃,该温度范围有利于针状铁素体组织均匀和细化,特别是避免M/A组元的长大和聚集,避免产生组织不均匀对抗SSC性能产生不利影响。
具体实施方式
本发明公开了一种690MPa级抗H2S应力腐蚀油套管用卷板及其制造方法。本领域技术人员可以借鉴本文内容,适当改进工艺参数实现。特别需要指出的是,所有类似的替换和改动对本领域技术人员来说是显而易见的,它们都被视为包括在本发明。本发明的方法及应用已经通过较佳实施例进行了描述,相关人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和应用进行改动或适当变更与组合,来实现和应用本发明技术。
一种690MPa级抗H2S应力腐蚀油套管用卷板,其化学成分按重量百分比为:
C:0.13%~0.17%,Si:0.15%~0.30%,Mn:1.40%~1.70%,P:≤0.013%,S:≤0.004%,Ti:0.01%~0.03%,Nb:0.06%~0.10%,V:0.04~0.08%,Mg:0.005%~0.007%,Zr:0.001%~0.004%,稀土元素:0.001%~0.003%,Al:0.02%~0.06%,N:≤0.008%,其余为Fe和不可避免元素。
与现有技术相比,本方案采用低碳含镁的Nb-V-Ti复合设计,材料的强度高,低温韧性更好,抗SSC性能优异;Mg细化夹杂物,可有效改变夹杂物形态和大小,对SSC性能和冲击有利;Nb和V有效提高强度,且提高抗SSC性能;Pcm低于0.25%,焊接性良好。
以下详细阐述本发明各合金成分作用机理,其中百分符号%代表重量百分比:
C:为碳化物形成元素,是保证强度的最有效元素,可以提高淬透性,保证材料强度和硬度。只有保证足够的碳,才会形成足够的富碳残余奥氏体并能够稳定至室温,最终形成少量均匀细小的M/A组织。如碳含量过低,无法保证材料的硬度,导致车丝性能差。含量过高,将影响产品的焊接性、塑性和冲击韧性,其最佳范围是0.13%~0.17%。
Si:可以溶入铁素体和奥氏体中,起到一定的固溶强化作用,可显著提高钢的硬度和强度,并提高疲劳强度和疲劳比,但含量过高会显著降低钢的塑性和韧性,其最佳范围是0.15%-0.30%。
Mn:锰具有固溶强化作用,还能增加奥氏体稳定性,对提高淬透性也有利,有效保证钢的强度。锰和铁形成人固溶体,提高钢中铁素体和奥氏体硬度和强度,同时又是碳化物形成元素,进入渗碳体取代一部分铁原子,锰在钢中由于降低临界转变温度;可使C曲线右移,促进贝氏体转化。但锰含量过大,可增加连铸坯的中心偏析倾向,会使钢板中带状组织增多,最终钢板中会含有一定量的带状组织,使钢板的脆性增加,塑性降低,抗腐蚀性能变差。同时,形成易于形成MnS,对抗HIC性能影响恶劣,其最佳范围是1.40%-1.70%。
P、S、N:是钢中不可避免的杂质元素,希望越低越好,但要求过低会增加生产成本,本发明的P≤0.013%、S≤0.004%、N≤0.006%。
Ti:钛是强的固氮元素,加入0.015%左右Ti时,可在板坯连铸时形成高温稳定细小的TiN析出相,这种细小的TiN析出相可有效阻止连铸坯在加热过程中奥氏体晶粒的长大,同时对改善钢焊接时热影响区的韧性有明显作用。析出的TiC产生较强的沉淀强化作用可以保证钢管后续正火热处理晶粒不明显长大,从而保证了整管热处理后的强度满足N80高强度性能要求。但含量过高则合金成本偏高。其最佳范围是0.01%-0.03%。
Nb:铌是细晶和析出强化元素,可弥补因碳降低而引起的强度的下降,改善冲击性能;在加热和热轧阶段起到一定的阻止晶粒长大作用,从而细化淬火后晶粒,保证冲击韧性,使钢具有更高强度和高韧性;但过高会增加合金成本,合适的范围是0.06%-0.10%。
V:钒缩小奥氏体相区,在σ铁中无限固溶,是强碳化物和氮化物形成元素。固溶于奥氏体中可以提高钢的淬透性;固溶于铁素体中有极强的固溶强化作用,有效提高抗拉强度,降低屈强比。有细化晶粒作用,所以对低温冲击韧性有利。钒与碳形成碳化物,在高温高压下可提高抗氢腐蚀能力。合适的范围是0.04%-0.08%。
Mg:镁有强化学活性,与氧、硫有很强的亲和力,是有效精炼剂,可降低钢中氧、硫含量和夹杂物数量,纯净钢液,还能对钢中夹杂物起到明显的变性作用,改善钢的性能。微量镁可改变硫化物、碳化物、碳氮化物的数量,种类,尺寸,分布。镁处理的夹杂物是混合相,其核心是含镁氧化物,该结构细小弥散分布在钢中,形成符合夹杂物,改善钢材性能和抗腐蚀性能。合适的范围是0.005%-0.007%。
Zr:微量锆具有脱氧、净化、细化晶粒及对夹杂物具有明显的变质作用,提高钢的低温韧性。与Cr混合加入,可显著抑制合金的再结晶,提高合金抗SSC腐蚀能力。其最佳范围是0.001%-0.004%。
稀土元素:可使钢中硫化物变得微细,提高钢的耐SSC性能,还可以与P结合,抑制P的偏析,可抑制由P的偏析引起的耐SSC性能的下降。但含量过高时,氧化物开始粗大,耐SSC性能下降。其最佳范围是0.001%-0.003%。
Al:铝是常用的脱氧剂,在钢中加入少量的铝,可细化晶粒,提高冲击韧性,本发明的Als含量为0.02%-0.05%。
一种690MPa级抗H2S应力腐蚀油套管用卷板的制造方法,包括铁水预处理、钢水冶炼、炉外精炼和板坯连铸、连铸坯再加热、轧制、冷却、卷取,具体包括如下步骤:
1)冶炼连铸工艺:
铁水预处理,转炉冶炼-经顶吹或顶底复合吹炼,炉外精炼、LF炉轻脱硫处理及进行钙处理以控制夹杂物形态和提高钢的延展性、韧性和冷弯性能,板坯连铸制成连铸板坯-连铸采用电磁搅拌或动态轻压下、以提高连铸板坯的质量。
2)轧制、冷却工艺:连铸板坯经加热炉加热至1210-1280℃,随后采用热机械轧制。粗轧终轧温度1020-1060℃,精轧开轧温度960-990℃,终轧温度830-880℃,该轧制温度范围有利于Nb、V、Ti不同阶段的充分析出,细化晶粒尺寸,提高强度和韧性;轧后钢带以26-29℃/s的速度进行冷却,该冷却速度下,能够获得完全的针状铁素体组织,该组织强度韧性匹配最好,可明显提高强度和韧性;同时该冷速对细化最终组织有利,减少制管时包申格效应造成的屈服强度下降,还可以减轻带状组织到0.5级以下,提高抗SSC腐蚀性能。冷却后进行卷取,卷取温度400-450℃,该温度范围有利于针状铁素体组织均匀和细化,特别是避免M/A组元的长大和聚集,避免产生组织不均匀对抗SSC性能产生不利影响。
3)卷板的最终组织为针状铁素体;Pcm低于0.25%,A/B/C/D类夹杂物级别1.0级以下,各类和值级别1.5级以下,带状组织0.5级以下。
【实施例】
一种690MPa级抗H2S应力腐蚀油套管用卷板及其制造方法,具体实施方式如下:
其中表1为实施例卷板的化学成分;表2为实施例加热、轧制、冷却工艺参数;表3为实施例力学性能检测结果。
表1实施例化学成分(wt%)
表2加热、轧制、冷却工艺参数
表3力学和耐腐蚀性能表
由表1~3可见,采用本发明的成分设计和轧制、卷取工艺,生产出的690MPa级抗H2S应力腐蚀油套管用卷板,满足API SPEC 5CT标准N80级力学性能和耐腐蚀性能的要求。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (5)
1.一种690MPa级抗H2S应力腐蚀油套管用卷板,其特征在于,其化学成分按重量百分比为:
C:0.13%~0.17%,Si:0.15%~0.30%,Mn:1.40%~1.70%,P:≤0.013%,S:≤0.004%,Ti:0.01%~0.03%,Nb:0.06%~0.10%,V:0.04%~0.08%,Mg:0.005%~0.007%,Zr:0.001%~0.004%,稀土元素:0.001%~0.003%,Al:0.02%~0.06%,N:≤0.008%,Pcm低于0.25%,其余为Fe和不可避免元素。
2.根据权利要求1所述的一种690MPa级抗H2S应力腐蚀油套管用卷板,其特征在于,卷板的最终组织为针状铁素体;A/B/C/D类夹杂物级别1.0级以下,各类和值级别1.5级以下,带状组织0.5级以下,-10℃冲击功大于180J。
3.一种如权利要求1所述690MPa级抗H2S应力腐蚀油套管用卷板的制造方法,其特征在于,具体包括如下步骤:
1)冶炼连铸:
炉外精炼、LF炉轻脱硫处理及进行钙处理,
板坯连铸制成连铸坯,连铸采用电磁搅拌或动态轻压下;
2)轧制:
连铸板坯加热至1210~1280℃,随后采用热机械轧制,
粗轧终轧温度1020~1060℃,精轧开轧温度960~990℃,终轧温度830~880℃;
3)冷却:
轧后采用层流冷却,冷却速度为26~30℃/s;
4)卷取:
冷却后进行卷取,卷取温度400~450℃。
4.根据权利要求3所述的一种690MPa级抗H2S应力腐蚀油套管用卷板的制造方法,其特征在于,所述1)转炉冶炼经顶吹或顶底复合吹炼。
5.根据权利要求3所述的一种690MPa级抗H2S应力腐蚀油套管用卷板的制造方法,其特征在于,所述2)连铸板坯经加热炉加热至1210~1280。
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